Microscopic origin of entropy-driven polymorphism in hybrid organic-inorganic perovskite materials

Keith T. Butler, Katrine Svane, Gregor Kieslich, Anthony K. Cheetham, Aron Walsh

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Abstract

Entropy is a critical, but often overlooked, factor in determining the relative stabilities of crystal phases. The importance of entropy is most pronounced in softer materials, where small changes in free energy can drive phase transitions, which has recently been demonstrated in the case of organic-inorganic hybrid-formate perovskites. In this Rapid Communication we demonstrate the interplay between composition and crystal structure that is responsible for the particularly pronounced role of entropy in determining polymorphism in hybrid organic-inorganic materials. Using ab initio based lattice dynamics, we probe the origins and effects of vibrational entropy of four archetype perovskite (ABX3) structures. We consider an inorganic material (SrTiO3), an A-site hybrid-halide material (CH3NH3)PbI3, a X-site hybrid material KSr(BH4)3, and a mixed A- and X-site hybrid-formate material (N2H5)Zn(HCO2)3, comparing the differences in entropy between two common polymorphs. The results demonstrate the importance of low-frequency intermolecular modes in determining the phase stability in these materials. The understanding gained allows us to propose a general principle for the relative stability of different polymorphs of hybrid materials as temperature is increased.

Original languageEnglish
Article number180103
JournalPhysical Review B : Condensed Matter and Materials Physics
Volume94
Issue number18
DOIs
Publication statusPublished - 1 Nov 2016

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inorganic materials
polymorphism
Polymorphism
formic acid
Perovskite
Entropy
entropy
Hybrid materials
formates
Lattice vibrations
Phase stability
perovskites
Free energy
halides
Crystal structure
Phase transitions
communication
free energy
perovskite
low frequencies

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Microscopic origin of entropy-driven polymorphism in hybrid organic-inorganic perovskite materials. / Butler, Keith T.; Svane, Katrine; Kieslich, Gregor; Cheetham, Anthony K.; Walsh, Aron.

In: Physical Review B : Condensed Matter and Materials Physics, Vol. 94, No. 18, 180103, 01.11.2016.

Research output: Contribution to journalArticle

Butler, Keith T. ; Svane, Katrine ; Kieslich, Gregor ; Cheetham, Anthony K. ; Walsh, Aron. / Microscopic origin of entropy-driven polymorphism in hybrid organic-inorganic perovskite materials. In: Physical Review B : Condensed Matter and Materials Physics. 2016 ; Vol. 94, No. 18.
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